Nonaqueous, particulate-containing detergent compositions

ABSTRACT

Nonaqueous detergent compositions which are in the form of a liquid, paste or gel, wherein the compositions comprise a divalent and/or trivalent metal salt bleach activator are disclosed.

FIELD OF THE INVENTION

This invention relates to nonaqueous laundry detergent products whichare in the form of a liquid, gel or paste and which are in the form ofstable dispersions of particulate material such as bleaching agents andbleach activators.

BACKGROUND OF THE INVENTION

Detergent products in the form of liquid, gel or paste are oftenconsidered to be more convenient to use than are dry powdered orparticulate detergent products. Said detergents have therefore foundsubstantial favor with consumers. Such detergent products are readilymeasurable, speedily dissolved in the wash water, capable of beingeasily applied in concentrated solutions or dispersions to soiled areason garments to be laundered and are non-dusting. They also usuallyoccupy less storage space than granular products. Additionally, suchdetergents may have incorporated in their formulations materials whichcould not withstand drying operations without deterioration, whichoperations are often employed in the manufacture of particulate orgranular detergent products.

Although said detergents have a number of advantages over granulardetergent products, they also inherently possess several disadvantages.In particular, detergent composition components which may be compatiblewith each other in granular products may tend to interact or react witheach other. Thus such components as enzymes, surfactants, perfumes,brighteners, solvents and especially bleaches and bleach activators canbe especially difficult to incorporate into liquid detergent productswhich have an acceptable degree of chemical stability.

One approach for enhancing the chemical compatibility of detergentcomposition components in detergent products has been to formulatenonaqueous (or anhydrous) detergent compositions. In such nonaqueousproducts, at least some of the normally solid detergent compositioncomponents tend to remain insoluble in the liquid product and hence areless reactive with each other than if they had been dissolved in theliquid matrix. Nonaqueous liquid detergent compositions, including thosewhich contain reactive materials such as peroxygen bleaching agents,have been disclosed for example, in Hepworth et al., U.S. Pat. No.4,615,820, Issued Oct. 17, 1986; Schultz et al., U.S. Pat. No.4,929,380, Issued May 29, 1990; Schultz et al., U.S. Pat. No. 5,008,031,Issued Apr. 16, 1991; Elder et al., EP-A-030,096, Published Jun. 10,1981; Hall et al., WO 92/09678, Published Jun. 11, 1992 and Sanderson etal., EP-A-565,017, Published Oct. 13, 1993.

Difficulties that have been observed with the incorporation of bleachactivators in non-aqueous detergents, include the chemical and/orphysical stability of the bleach activators. EP 339 995 describes anon-aqueous liquid detergent composition comprising a persalt bleach anda precursor therefore, the composition containing a capped alkoxylatednonionic surfactant. EP 540 090 proposes to use a bleach precursor whichis relatively insoluble in the non aqueous liquid phase of the liquiddetergent composition.

A difficulty associated with the stability of bleach activators is that,upon dilution in the wash liquor, the bleach activators still need tohave a certain degree of solubility high enough to be effective as ableaching species in the wash liquor.

Given the foregoing, there is clearly a continuing need to identify andprovide nonaqueous, bleach activator-containing detergent compositionsin the form of liquid, gel or paste products that have a high degree ofchemical stability in the concentrate along with an efficient bleachingperformance in the wash liquor.

Accordingly, it is an object of the present invention to provide anon-aqueous detergent composition wherein the bleach activators arechemically stable in the concentrate, while at the same time still beingeffective as bleach species in the wash liquor.

According to the present invention, there is provided a nonaqueousdetergent composition which is in the form of a liquid, gel or paste,containing a bleaching agent and a bleach activator which is present asa divalent metal salt, a trivalent metal salt, a mixed metal saltwhereby at least one of the salts is a divalent or a trivalent metalsalt, or mixtures thereof.

SUMMARY OF THE INVENTION

The present invention provides a nonaqueous heavy-duty detergentcomposition which is in the form of a liquid, gel or paste, saidcomposition comprising a bleaching agent and a bleach activator,characterized in that said bleach activator is present as a divalentmetal salt, a trivalent metal salt, a mixed metal salt whereby at leastone of the salts is a divalent or a trivalent metal salt, or mixturesthereof.

DETAILED DESCRIPTION OF THE INVENTION

1. Bleaching Agents and Bleach Activators

The bleaching agents used herein can be any of the bleaching agentsuseful for detergent or bleaching compositions in textile cleaning, hardsurface cleaning, or other cleaning purposes that are now known orbecome known, and are useful for bleaching compositions as used in thepresent invention to treat fabrics. These include oxygen bleaches aswell as other bleaching agents. Perborate bleaches, e.g., sodiumperborate (e.g., mono- or tetrahydrate) can be used herein.

Peroxygen bleaching agents are preferably used in the compositions.Suitable peroxygen bleaching compounds include perborate, sodiumcarbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodiumpyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) canalso be used.

The bleach activators according to the present invention are present asa divalent and/or trivalent metal salt. The bleach activator salt can beadded as a powder dispersed in the non-aqueous base. The bleachactivator salt can also be premixed with a liquid non-aqueous ingredientsuch as a nonionic surfactant, organic solvent and/or mixtures thereof.The bleach activator salts can be obtained by any method known toprepare divalent metal salts of anionic surface active solutions.

The bleach activator salts of the present invention can comprise mixedsalts whereby at least one of the salts is a divalent or trivalent salt.The mixed salts are obtained by cocrystallization of the bleachactivator salts. The mixed salts can comprise a monovalent salt.Examples of these salts are Na₃ Mg 4- N-nonanoyl-6-aminohexanoyloxybenzene sulfonate!₅.

Preferred salts according to the present invention are Ca, Mg and Alsalts. Highly preferred are Ca and Mg salts or mixtures thereof.

The bleach activators suitable for the present invention are the anionicbleach activators described in the literature, such as in the GB Patents836,988; 864,798; 907,356; 1,003,310 and 1,519,351; German Patent3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591; and U.S. Pat. Nos.1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.

A class of anionic bleach activators is that as disclosed in U.S. Pat.Nos. 4,751,015 and 4,397,757, in EP-A-284292, EP-A-331,229 andEP-A-03520. Examples of anionic peroxyacid bleach activators includesodium-4-benzoyloxy benzene sulphonate; sodium-1-methyl-2-benzoyloxybenzene-4-sulphonate; sodium nonanoyloxybenzene sulphonate; sodium3,5,5,-trimethyl hexanoyloxybenzene sulphonate.

Bleach activators also useful in the present invention are amidesubstituted compounds of the general formulas: ##STR1## or mixturesthereof, wherein R¹ is an alkyl, aryl, or alkaryl group containing fromabout 1 to about 14 carbon atoms, R² is an alkylene, arylene oralkarylene group containing from about 1 to about 14 carbon atoms, R⁵ isH or an alkyl, aryl, or alkaryl group containing from about 1 to about10 carbon atoms, and L can be essentially any suitable leaving group. Aleaving group is any group that is displaced from the bleachingactivator as a consequence of the nucleophilic attack on the bleachactivator by the perhydroxide anion. This, the perhydrolysis reaction,results in the formation of the peroxycarboxylic acid. Generally, for agroup to be a suitable leaving group it must exert an electronattracting effect. It should also form a stable entity so that the rateof the back reaction is negligible. This facilitates the nucleophilicattack by the perhydroxide anion.

The L group must be sufficiently reactive for the reaction to occurwithin the optimum time frame (e.g., a wash cycle) . However, if L istoo reactive, this activator will be difficult to stabilize for use in ableaching composition. These characteristics are generally paralleled bythe pKa of the conjugate acid of the leaving group, although exceptionsto this convention are known. Ordinarily, leaving groups that exhibitsuch behavior are those in which their conjugate acid has a pKa in therange of from about 4 to about 13, preferably from about 6 to about 11and most preferably from about 8 to about 11.

Preferred bleach activators are those of the above general formulawherein R¹, R² and R⁵ are as defined for the peroxyacid and L isselected from the group consisting of: ##STR2## and mixtures thereof,wherein R¹ is an alkyl, aryl, or alkaryl group containing from about 1to about 14 carbon atoms, R³ is an alkyl chain containing from 1 toabout 8 carbon atoms, R⁴ is H or R³, and Y is a solubilizing anionicgroup.

The solubilizing groups are --SO₃ ⁻, --CO₂ ⁻, --SO₄ ⁻, and mostpreferably --SO₃ ⁻ and --CO₂ ⁻ wherein R³ is an alkyl chain containingfrom about 1 to about 4 carbon atoms.

Preferred anionic bleach activators are those of the above generalformula wherein L is selected from the group consisting of: ##STR3##wherein R³ is as defined above and Y is --SO₃ ⁻ or --CO₂ ⁻.

Preferred examples of bleach activators of the above formulae include 4-N-octanoyl-6-aminohexanoyloxy!benzene sulfonate, 4-N-nonanoyl-6-aminohexanoyloxy!benzene sulfonate, 4-N-decanoyl-6-aminohexanoyloxy!benzene sulfonate and mixtures thereof.Said activators are described in U.S. Pat. No. 4,634,551 and U.S. Pat.No. 4,852,989.

Another important class of anionic bleach activators provide organicperacids as described herein by ring-opening as a consequence of thenucleophilic attack on the carbonyl carbon of the cyclic ring by theperhydroxide anion. For instance, this ring-opening reaction in certainactivators involves attack at the lactam ring carbonyl by hydrogenperoxide or its anion. Since attack of an acyl lactam by hydrogenperoxide or its anion occurs preferably at the exocyclic carbonyl,obtaining a significant fraction of ring-opening may require a catalyst.Another example of ring-opening bleach activators can be found in otheractivators, such as those disclosed in U.S. Pat. No. 4,966,723, Hodge etal, issued Oct. 30, 1990.

Surprisingly, it has now been found that the bleach activators of thepresent invention in contrast with monovalent bleach activator salts,are chemically stable in the concentrate, while at the same time beingeffective as a bleach species in the wash liquor.

In addition, it has been found that bleach activators, when agglomeratedwith certain acid such as citric acid, are more chemically stable.

The nonaqueous detergent compositions of this invention may furthercomprise a surfactant- and low-polarity solvent-containing liquid gelphase having dispersed therein the bleach activator salt. The componentsof the liquid and solid phases of the detergent compositions herein, aswell as composition form, preparation and use, are described in greaterdetail as follows:

All concentrations and ratios are on a weight basis unless otherwisespecified.

Surfactant

The amount of the surfactant mixture component of the detergentcompositions herein can vary depending upon the nature and amount ofother composition components and depending upon the desired Theologicalproperties of the ultimately formed composition. Generally, thissurfactant mixture will be used in an amount comprising from about 10%to 90% by weight of the composition. More preferably, the surfactantmixture will comprise from about 15% to 50% by weight of thecomposition.

A typical listing of anionic, nonionic, ampholytic and zwitterionicclasses, and species of these surfactants, is given in U.S. Pat. No.3,664,961 issued to Norris on May 23, 1972.

Preferred anionic surfactants include the alkyl sulfate surfactantshereof are water soluble salts or acids of the formula ROSO₃ M wherein Rpreferably is a C₁₀ -C₂₄ hydrocarbyl, preferably an alkyl orhydroxyalkyl having a C₁₀ -C₁₈ alkyl component, more preferably a C₁₂-C₁₅ alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkalimetal cation (e.g. sodium, potassium, lithium), or ammonium orsubstituted ammonium (quaternary ammonium cations such astetramethyl-ammonium and dimethyl piperdinium cations).

Highly preferred anionic surfactants include alkyl alkoxylated sulfatesurfactants hereof are water soluble salts or acids of the formulaRO(A)_(m) SO3M wherein R is an unsubstituted C₁₀ -C₂₄ alkyl orhydroxyalkyl group having a C₁₀ -C₂₄ alkyl component, preferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, more preferably C₁₂ -C₁₅ alkyl orhydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero,typically between about 0.5 and about 6, more preferably between about0.5 and about 3, and M is H or a cation which can be, for example, ametal cation (e.g., sodium, potassium, lithium, calcium, magnesium,etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylatedsulfates as well as alkyl propoxylated sulfates are contemplated herein.Specific examples of substituted ammonium cations include quaternaryammonium cations such as tetramethyl-ammonium and dimethyl piperdiniumcations Exemplary surfactants are C₁₂ -C₁₅ alkyl polyethoxylate (1.0)sulfate (C₁₂ -C₁₅ E(1.0)M), C₁₂ -C₁₅ alkyl polyethoxylate (2.25) sulfate(C₁₂ -C₁₅ E(2.25)M), C₁₂ -C₁₅ alkyl polyethoxylate (3.0) sulfate (C₁₂-C₁₅ E(3.0)M), and C₁₂ -C₁₅ alkyl polyethoxylate (4.0) sulfate (C₁₂ -C₁₅E(4.0)M), wherein M is conveniently selected from sodium and potassium.

Other suitable anionic surfactants to be used are alkyl ester sulfonatesurfactants including linear esters of C₈ -C₂₀ carboxylic acids (i.e.,fatty acids) which are sulfonated with gaseous SO₃ according to "TheJournal of the American Oil Chemists Society", 52 (1975), pp. 323-329.Suitable starting materials would include natural fatty substances asderived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundryapplications, comprise alkyl ester sulfonate surfactants of thestructural formula: ##STR4## wherein R³ is a C₈ -C₂₀ hydrocarbyl,preferably an alkyl, or combination thereof, R⁴ is a C₁ -C₆ hydrocarbyl,preferably an alkyl, or combination thereof, and M is a cation whichforms a water soluble salt with the alkyl ester sulfonate. Suitablesalt-forming cations include metals such as sodium, potassium, andlithium, and substituted or unsubstituted ammonium cations. Preferably,R³ is C₁₀ -C₁₆ alkyl, and R⁴ is methyl, ethyl or isopropyl. Especiallypreferred are the methyl ester sulfonates wherein R³ is C₁₀ -C₁₆ alkyl.

Other anionic surfactants useful for detersive purposes can also beincluded in the laundry detergent compositions of the present invention.These can include salts (including, for example, sodium, potassium,ammonium, and substituted ammonium salts such as mono-, di- andtriethanolamine salts) of soap, C₉ -C₂₀ linear alkylbenzenesulfonates,C₈ -C₂₂ primary of secondary alkanesulfonates, C₈ -C₂₄ olefinsulfonates,sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzedproduct of alkaline earth metal citrates, e.g., as described in Britishpatent specification No. 1,082,179, C₈ -C₂₄ alkylpolyglycolethersulfates(containing up to 10 moles of ethylene oxide); alkyl glycerolsulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerolsulfates, alkyl phenol ethylene oxide ether sulfates, paraffinsulfonates, alkyl phosphates, isethionates such as the acylisethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates,monoesters of sulfosuccinates (especially saturated and unsaturated C₁₂-C₁₈ monoesters) and diesters of sulfosuccinates (especially saturatedand unsaturated C₆ -C₁₂ diesters), sulfates of alkylpolysaccharides suchas the sulfates of alkylpolyglucoside (the nonionic nonsulfatedcompounds being described below), and alkyl polyethoxy carboxylates suchas those of the formula RO(CH₂ CH₂ O)_(k) --CH₂ COO--M+ wherein R is aC₈ -C₂₂ alkyl, k is an integer from 1 to 10, and M is a solublesalt-forming cation. Resin acids and hydrogenated resin acids are alsosuitable, such as rosin, hydrogenated rosin, and resin acids andhydrogenated resin acids present in or derived from tall oil. Furtherexamples are described in "Surface Active Agents and Detergents" (Vol. Iand II by Schwartz, Perry and Berch). A variety of such surfactants arealso generally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30,1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line23 (herein incorporated by reference).

When included therein, the detergent compositions of the presentinvention typically comprise from about 1% to about 40%, preferably fromabout 5% to about 25% by weight of such anionic surfactants.

One class of nonionic surfactants useful in the present invention arecondensates of ethylene oxide with a hydrophobic moiety to provide asurfactant having an average hydrophilic-lipophilic balance (HLB) in therange from 8 to 17, preferably from 9.5 to 14, more preferably from 12to 14. The hydrophobic (lipophilic) moiety may be aliphatic or aromaticin nature and the length of the polyoxyethylene group which is condensedwith any particular hydrophobic group can be readily adjusted to yield awater-soluble compound having the desired degree of balance betweenhydrophilic and hydrophobic elements.

Especially preferred nonionic surfactants of this type are the C₉ -C₁₅primary alcohol ethoxylates containing 3-12 moles of ethylene oxide permole of alcohol, particularly the C₁₂ -C₁₅ primary alcohols containing5-8 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfactants comprises alkyl polyglucosidecompounds of general formula

    RO (C.sub.n H.sub.2n O).sub.t Z.sub.x

wherein Z is a moiety derived from glucose; R is a saturated hydrophobicalkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10and n is 2 or 3; x is from 1.3 to 4, the compounds including less than10% unreacted fatty alcohol and less than 50% short chain alkylpolyglucosides. Compounds of this type and their use in detergent aredisclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.

Also suitable as nonionic surfactants are poly hydroxy fatty acid amidesurfactants of the formula ##STR5## wherein R¹ is H, or R¹ is C₁₋₄hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R²is C₅₋₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linearhydrocarbyl chain with at least 3 hydroxyls directly connected to thechain, or an alkoxylated derivative thereof. Preferably, R¹ is methyl,R² is a straight C₁₁₋₁₅ alkyl or alkenyl chain such as coconut alkyl ormixtures thereof, and Z is derived from a reducing sugar such asglucose, fructose, maltose, lactose, in a reductive amination reaction.

Nonaqueous Liquid Diluent

To form the liquid gel of paste phase of the detergent compositions, thehereinbefore described surfactant (mixture) may be combined with anonaqueous liquid diluent such as a liquid alcohol alkoxylate materialor a nonaqueous, low-polarity organic solvent.

Alcohol Alkoxylates

One component of the liquid diluent suitable to form the compositionsherein comprises an alkoxylated fatty alcohol material. Such materialsare themselves also nonionic surfactants. Such materials correspond tothe general formula:

    R.sup.1 (C.sub.m H.sub.2m O).sub.n OH

wherein R¹ is a C₈ -C₁₆ alkyl group, m is from 2 to 4, and n ranges fromabout 2 to 12. Preferably R¹ is an alkyl group, which may be primary orsecondary, that contains from about 9 to 15 carbon atoms, morepreferably from about 10 to 14 carbon atoms. Preferably also thealkoxylated fatty alcohols will be ethoxylated materials that containfrom about 2 to 12 ethylene oxide moieties per molecule, more preferablyfrom about 3 to 10 ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol component of the liquid diluent willfrequently have a hydrophilic-lipophilic balance (HLB) which ranges fromabout 3 to 17. More preferably, the HLB of this material will range fromabout 6 to 15, most preferably from about 8 to 15.

Examples of fatty alcohol alkoxylates useful as one of the essentialcomponents of the nonaqueous liquid diluent in the compositions hereinwill include those which are made from alcohols of 12 to 15 carbon atomsand which contain about 7 moles of ethylene oxide. Such materials havebeen commercially marketed under the trade names Neodol 25-7 and Neodol23-6.5 by Shell Chemical Company. Other useful Neodols include Neodol1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkylchain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylatedprimary C₁₂ -C₁₃ alcohol having about 9 moles of ethylene oxide andNeodol 91-10, an ethoxylated C₉ -C₁₁ primary alcohol having about 10moles of ethylene oxide. Alcohol ethoxylates of this type have also beenmarketed by Shell Chemical Company under the Dobanol tradename. Dobanol91-5 is an ethoxylated C₉ -C₁₁ fatty alcohol with an average of 5 molesethylene oxide and Dobanol 25-7 is an ethoxylated C₁₂ -C₁₅ fatty alcoholwith an average of 7 moles of ethylene oxide per mole of fatty alcohol.

Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7and Tergitol 15-S-9 both of which are linear secondary alcoholethoxylates that have been commercially marketed by Union CarbideCorporation. The former is a mixed ethoxylation product of C₁₁ to C₁₅linear secondary alkanol with 7 moles of ethylene oxide and the latteris a similar product but with 9 moles of ethylene oxide being reacted.

Other types of alcohol ethoxylates useful in the present compositionsare higher molecular weight nonionics, such as Neodol 45-11, which aresimilar ethylene oxide condensation products of higher fatty alcohols,with the higher fatty alcohol being of 14-15 carbon atoms and the numberof ethylene oxide groups per mole being about 11. Such products havealso been commercially marketed by Shell Chemical Company.

The alcohol alkoxylate component when utilized as part of the liquiddiluent in the nonaqueous compositions herein will generally be presentto the extent of from about 1% to 60% by weight of the composition. Morepreferably, the alcohol alkoxylate component will comprise about 5% to40% by weight of the compositions herein. Most preferably, the alcoholalkoxylate component will comprise from about 10% to 25% by weight ofthe detergent compositions herein.

Nonaqueous Low-Polarity Organic Solvent

Another component of the liquid diluent which may form part of thedetergent compositions herein comprises nonaqueous, low-polarity organicsolvent(s). The term "solvent" is used herein to connote the non-surfaceactive carrier or diluent portion of the liquid phase of thecomposition. While some of the essential and/or optional components ofthe compositions herein may actually dissolve in the"solvent"-containing phase, other components will be present asparticulate material dispersed within the "solvent"-containing phase.Thus the term "solvent" is not meant to require that the solventmaterial be capable of actually dissolving all of the detergentcomposition components added thereto.

The nonaqueous organic materials which are employed as solvents hereinare those which are liquids of low polarity. For purposes of thisinvention, "low-polarity" liquids are those which have little, if any,tendency to dissolve one of the preferred types of particulate materialused in the compositions herein, i.e., the peroxygen bleaching agents,sodium perborate or sodium percarbonate. Thus relatively polar solventssuch as ethanol should not be utilized. Suitable types of low-polaritysolvents useful in the nonaqueous liquid detergent compositions hereindo include alkylene glycol mono lower alkyl ethers, lower molecularweight polyethylene glycols, lower molecular weight methyl esters andamides, and the like.

A preferred type of nonaqueous, low-polarity solvent for use hereincomprises the mono-, di-, tri-, or tetra-C₂ -C₃ alkylene glycol mono C₂-C₆ alkyl ethers. The specific examples of such compounds includediethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether,dipropolyene glycol monoethyl ether, and dipropylene glycol monobutylether. Diethylene glycol monobutyl ether and dipropylene glycolmonobutyl ether are especially preferred. Compounds of the type havebeen commercially marketed under the tradenames Dowanol, Carbitol, andCellosolve.

Another preferred type of nonaqueous, low-polarity organic solventuseful herein comprises the lower molecular weight polyethylene glycols(PEGs). Such materials are those having molecular weights of at leastabout 150. PEGs of molecular weight ranging from about 200 to 600 aremost preferred.

Yet another preferred type of non-polar, nonaqueous solvent compriseslower molecular weight methyl esters. Such materials are those of thegeneral formula: R¹ --C(O)--OCH₃ wherein R¹ ranges from 1 to about 18.Examples of suitable lower molecular weight methyl esters include methylacetate, methyl propionate, methyl octanoate, and methyl dodecanoate.

The nonaqueous, low-polarity organic solvent(s) employed should, ofcourse, be compatible and non-reactive with other compositioncomponents, e.g., bleach and/or activators, used in the liquid detergentcompositions herein. Such a solvent component will generally be utilizedin an amount of from about 1% to 60% by weight of the composition. Morepreferably, the nonaqueous, low-polarity organic solvent will comprisefrom about 5% to 40% by weight of the composition, most preferably fromabout 10% to 25% by weight of the composition.

Liquid Diluent Concentration

As with the concentration of the surfactant mixture, the amount of totalliquid diluent in the compositions herein will be determined by the typeand amounts of other composition components and by the desiredcomposition properties. Generally, the liquid diluent will comprise fromabout 20% to 80% by weight of the compositions herein. More preferably,the liquid diluent will comprise from about 40% to 60% by weight of thecomposition.

SOLID PHASE

The nonaqueous detergent compositions herein may further comprise asolid phase of particulate material which is dispersed and suspendedwithin the liquid phase. Generally such particulate material will rangein size from about 0.1 to 1500 microns. More preferably such materialwill range in size from about 5 to 200 microns.

The particulate material utilized herein can comprise one or more typesof detergent composition components which in particulate form aresubstantially insoluble in the nonaqueous liquid phase of thecomposition. The types of particulate materials which can be utilizedare described in detail as follows:

Surfactants

Another possible type of particulate material which can be suspended inthe nonaqueous liquid detergent compositions herein includes ancillaryanionic surfactants which are fully or partially insoluble in thenonaqueous liquid phase. The most common type of anionic surfactant withsuch solubility properties comprises primary or secondary alkyl sulfateanionic surfactants. Such surfactants are those produced by thesulfation of higher C₈ -C₂₀ fatty alcohols.

Conventional primary alkyl sulfate surfactants have the general formula

    ROSO.sub.3.sup.- M.sup.+

wherein R is typically a linear C₈ -C₂₀ hydrocarbyl group, which may bestraight chain or branched chain, and M is a water-solubilizing cation.Preferably R is a C₁₀ -C₁₄ alkyl, and M is alkali metal. Most preferablyR is about C₁₂ and M is sodium.

Conventional secondary alkyl sulfates may also be utilized as theessential anionic surfactant component of the solid phase of thecompositions herein. Conventional secondary alkyl sulfate surfactantsare those materials which have the sulfate moiety distributed randomlyalong the hydrocarbyl "backbone" of the molecule. Such materials may bedepicted by the structure

    CH.sub.3 (CH.sub.2).sub.n (CHOSO.sub.3.sup.- M.sup.+) (CH.sub.2).sub.m CH.sub.3

wherein m and n are integers of 2 or greater and the sum of m+n istypically about 9 to 15, and M is a water-solubilizing cation.

If utilized as all or part of the requisite particulate material,ancillary anionic surfactants such as alkyl sulfates will generallycomprise from about 1% to 10% by weight of the composition, morepreferably from about 1% to 5% by weight of the composition. Alkylsulfate used as all or part of the particulate material is prepared andadded to the compositions herein separately from the unalkoxylated alkylsulfate material which may form part of the alkyl ether sulfatesurfactant component essentially utilized as part of the liquid phaseherein.

Organic Builder Material

Another possible type of particulate material which can be suspended inthe nonaqueous liquid detergent compositions herein comprises an organicdetergent builder material which serves to counteract the effects ofcalcium, or other ion, water hardness encountered duringlaundering/bleaching use of the compositions herein. Examples of suchmaterials include the alkali metal, citrates, succinates, malonates,fatty acids, carboxymethyl succinates, carboxylates, polycarboxylatesand polyacetyl carboxylates. Specific examples include sodium, potassiumand lithium salts of oxydisuccinic acid, mellitic acid, benzenepolycarboxylic acids and citric acid. Other examples of organicphosphonate type sequestering agents such as those which have been soldby Monsanto under the Dequest tradename and alkanehydroxy phosphonates.Citrate salts are highly preferred.

Other suitable organic builders include the higher molecular weightpolymers and copolymers known to have builder properties. For example,such materials include appropriate polyacrylic acid, polymaleic acid,and polyacrylic/polymaleic acid copolymers and their salts, such asthose sold by BASF under the Sokalan trademark.

Another suitable type of organic builder comprises the water-solublesalts of higher fatty acids, i.e., "soaps". These include alkali metalsoaps such as the sodium, potassium, ammonium, and alkylolammonium saltsof higher fatty acids containing from about 8 to about 24 carbon atoms,and preferably from about 12 to about 18 carbon atoms. Soaps can be madeby direct saponification of fats and oils or by the neutralization offree fatty acids. Particularly useful are the sodium and potassium saltsof the mixtures of fatty acids derived from coconut oil and tallow,i.e., sodium or potassium tallow and coconut soap.

If utilized as all or part of the requisite particulate material,insoluble organic detergent builders can generally comprise from about2% to 20% by weight of the compositions herein. More preferably, suchbuilder material can comprise from about 4% to 10% by weight of thecomposition.

Inorganic Alkalinity Sources

Another possible type of particulate material which can be suspended inthe nonaqueous liquid detergent compositions herein can comprise amaterial which serves to render aqueous washing solutions formed fromsuch compositions generally alkaline in nature. Such materials may ormay not also act as detergent builders, i.e., as materials whichcounteract the adverse effect of water hardness on detergencyperformance.

Examples of suitable alkalinity sources include water-soluble alkalimetal carbonates, bicarbonates, borates, silicates and metasilicates.Although not preferred for ecological reasons, water-soluble phosphatesalts may also be utilized as alkalinity sources. These include alkalimetal pyrophosphates, orthophosphates, polyphosphates and phosphonates.Of all of these alkalinity sources, alkali metal carbonates such assodium carbonate are the most preferred.

The alkalinity source, if in the form of a hydratable salt, may alsoserve as a desiccant in the nonaqueous liquid detergent compositionsherein. The presence of an alkalinity source which is also a desiccantmay provide benefits in terms of chemically stabilizing thosecomposition components such as the peroxygen bleaching agent which maybe susceptible to deactivation by water.

If utilized as all or part of the particulate material component, thealkalinity source will generally comprise from about 1% to 15% by weightof the compositions herein. More preferably, the alkalinity source cancomprise from about 2% to 10% by weight of the composition. Suchmaterials, while water-soluble, will generally be insoluble in thenonaqueous detergent compositions herein. Thus such materials willgenerally be dispersed in the nonaqueous liquid phase in the form ofdiscrete particles.

OPTIONAL COMPOSITION COMPONENTS

In addition to the composition liquid and solid phase components ashereinbefore described, the detergent compositions herein can, andpreferably will, contain various optional components. Such optionalcomponents may be in either liquid or solid form. The optionalcomponents may either dissolve in the liquid phase or may be dispersedwithin the liquid phase in the form of fine particles or droplets. Someof the materials which may optionally be utilized in the compositionsherein are described in greater detail as follows:

Optional Inorganic Detergent Builders

The detergent compositions herein may also optionally contain one ormore types of inorganic detergent builders beyond those listedhereinbefore that also function as alkalinity sources. Such optionalinorganic builders can include, for example, aluminosilicates such aszeolites. Aluminosilicate zeolites, and their use as detergent buildersare more fully discussed in Corkill et al., U.S. Pat. No. 4,605,509;Issued Aug. 12, 1986, the disclosure of which is incorporated herein byreference. Also crystalline layered silicates, such as those discussedin this '509 U.S. patent, are also suitable for use in the detergentcompositions herein. If utilized, optional inorganic detergent builderscan comprise from about 2% to 15% by weight of the compositions herein.

Optional Enzymes

The detergent compositions herein may also optionally contain one ormore types of detergent enzymes. Such enzymes can include proteases,amylases, cellulases and lipases. Such materials are known in the artand are commercially available. They may be incorporated into thenonaqueous liquid detergent compositions herein in the form ofsuspensions, "marumes" or "prills". Another suitable type of enzymecomprises those in the form of slurries of enzymes in nonionicsurfactants. Enzymes in this form have been commercially marketed, forexample, by Novo Nordisk under the tradename "LDP."

Enzymes added to the compositions herein in the form of conventionalenzyme prills are especially preferred for use herein. Such prills willgenerally range in size from about 100 to 1,000 microns, more preferablyfrom about 200 to 800 microns and will be suspended throughout thenonaqueous liquid phase of the composition. Prills in the compositionsof the present invention have been found, in comparison with otherenzyme forms, to exhibit especially desirable enzyme stability in termsof retention of enzymatic activity over time. Thus, compositions whichutilize enzyme prills need not contain conventional enzyme stabilizingsuch as must frequently be used when enzymes are incorporated intoaqueous liquid detergents.

If employed, enzymes will normally be incorporated into the nonaqueousliquid compositions herein at levels sufficient to provide up to about10 mg by weight, more typically from about 0.01 mg to about 5 mg, ofactive enzyme per gram of the composition. Stated otherwise, thenonaqueous liquid detergent compositions herein will typically comprisefrom about 0.001% to 5%, preferably from about 0.01% to 1% by weight, ofa commercial enzyme preparation. Protease enzymes, for example, areusually present in such commercial preparations at levels sufficient toprovide from 0.005 to 0.1 Anson units (AU) of activity per gram ofcomposition.

Optional Chelating Agents

The detergent compositions herein may also optionally contain achelating agent which serves to chelate metal ions, e.g., iron and/ormanganese, within the nonaqueous detergent compositions herein. Suchchelating agents thus serve to form complexes with metal impurities inthe composition which would otherwise tend to deactivate compositioncomponents such as the peroxygen bleaching agent. Useful chelatingagents can include amino carboxylates, phosphonates, amino phosphonates,polyfunctionally-substituted aromatic chelating agents and mixturesthereof.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetraacetates,N-hydroxyethyl-ethylene-diaminetriacetates, nitrilotriacetates,ethylene-diamine tetrapropionates, triethylenetetraaminehexacetates,diethylenetriaminepentaacetates, ethylenediaminedisuccinates andethanoldiglycines. The alkali metal salts of these materials arepreferred.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of this invention when at least low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylene-phosphonates) as DEQUEST. Preferably,these amino phosphonates do not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Preferred chelating agents include hydroxyethyl-diphosphonic acid(HEDP), diethylene triamine penta acetic acid (DTPA), ethylenediaminedisuccinic acid (EDDS) and dipicolinic acid (DPA) and salts thereof. Thechelating agent may, of course, also act as a detergent builder duringuse of the compositions herein for fabric laundering/bleaching. Thechelating agent, if employed, can comprise from about 0.1% to 4% byweight of the compositions herein. More preferably, the chelating agentwill comprise from about 0.2% to 2% by weight of the detergentcompositions herein.

Optional Thickening, Viscosity Control and/or Dispersing Agents

The detergent compositions herein may also optionally contain apolymeric material which serves to enhance the ability of thecomposition to maintain its solid particulate components in suspension.Such materials may thus act as thickeners, viscosity control agentsand/or dispersing agents. Such materials are frequently polymericpolycarboxylates but can include other polymeric materials such aspolyvinylpyrrolidone (PVP) and polymeric amine derivatives such asquaternized, ethoxylated hexamethylene diamines.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarboxylates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein of monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight of the polymer.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom about 2,000 to 10,000, more preferably from about 4,000 to 7,000,and most preferably from about 4,000 to 5,000. Water-soluble salts ofsuch acrylic acid polymers can include, for example, the alkali metal,salts. Soluble polymers of this type are known materials. Use ofpolyacrylates of this type in detergent compositions has been disclosed,for example, Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967. Suchmaterials may also perform a builder function.

If utilized, the optional thickening, viscosity control and/ordispersing agents should be present in the compositions herein to theextent of from about 0.1% to 4% by weight. More preferably, suchmaterials can comprise from about 0.5% to 2% by weight of the detergentscompositions herein.

Optional Brighteners, Suds Suppressors and/or Perfumes

The detergent compositions herein may also optionally containconventional brighteners, suds suppressors, silicone oils, bleachcatalysts, and/or perfume materials. Such brighteners, suds suppressors,silicone oils, bleach catalysts, and perfumes must, of course, becompatible and non-reactive with the other composition components in anonaqueous environment. If present, brighteners suds suppressors and/orperfumes will typically comprise from about 0.1% to 2% by weight of thecompositions herein.

Suitable bleach catalysts include the manganese based complexesdisclosed in U.S. Pat. No. 5,246,621, U.S. Pat. No. 5,244,594, U.S. Pat.No. 5,114,606 and U.S. Pat. No. 5,114,611.

COMPOSITION FORM

The particulate-containing liquid detergent compositions of thisinvention are substantially nonaqueous (or anhydrous) in character.While very small amounts of water may be incorporated into suchcompositions as an impurity in the essential or optional components, theamount of water should in no event exceed about 5% by weight of thecompositions herein. More preferably, water content of the nonaqueousdetergent compositions herein will comprise less than about 1% byweight.

The particulate-containing nonaqueous detergent compositions herein willbe in the form of a liquid, gel or paste.

COMPOSITION PREPARATION AND USE

The nonaqueous detergent compositions herein can be prepared bycombining the bleach activator salts and optional components thereof inany convenient order and by mixing, e.g., agitating, the resultingcomponent combination to form the phase stable compositions herein.

The compositions of this invention, prepared as hereinbefore described,can be used to form aqueous washing solutions for use in the launderingand bleaching of fabrics. Generally, an effective amount of suchcompositions is added to water, preferably in a conventional fabriclaundering automatic washing machine, to form such aqueouslaundering/bleaching solutions. The aqueous washing/bleaching solutionso formed is then contacted, preferably under agitation, with thefabrics to be laundered and bleached therewith.

An effective amount of the liquid detergent compositions herein added towater to form aqueous laundering/bleaching solutions can compriseamounts sufficient to form from about 500 to 7,000 ppm of composition inaqueous solution. More preferably, from about 1,000 to 3,000 ppm of thedetergent compositions herein will be provided in aqueouswashing/bleaching solution.

EXAMPLE

The following example illustrates the compositions of the presentinvention, but is not necessarily meant to limit or otherwise define thescope of the invention herein.

A bleach-containing nonaqueous laundry detergent is prepared having thecomposition as set forth in Table I.

                  TABLE I                                                         ______________________________________                                        Component                Wt. %                                                ______________________________________                                        Liquid Base                                                                   C.sub.12-15 alkyl ether (EO = 3) sulfate Na salt                                                       17                                                   C.sub.12-14 N-methyl glucamide                                                                         9                                                    C.sub.12-14, EO = 5 alcohol ethoxylate                                                                 17                                                   N-Butoxy propoxy propanol (BPP)                                                                        24                                                   Perfume                  0.7                                                  Solids                                                                        Topped palm kernel fatty acid Na salt                                                                  5.7                                                  Trisodium Citrate        1.9                                                  Sodium percarbonate      9.4                                                  Sodium carbonate         7.5                                                  Sodium hydroxyethyl diphosphonate (HEDP)Na salt                                                        1.7                                                   4- N-nonanoyl-6-aminohexanoyloxy!benzene                                                              4.7                                                  sulfonate!.sub.2 Ca salt                                                      Brightener               0.2                                                  Silicone Oil DB-100      0.5                                                  Enzymes and minor        Up to 100%                                           ______________________________________                                    

This composition is a stable anhydrous liquid laundry detergent whereinthe bleach activator is stable in the concentrate and wherein the bleachactivator is effective in the wash liquor.

What is claimed is:
 1. A nonaqueous detergent composition which is inthe form of a liquid, paste or gel, said nonaqueous detergentcomposition comprising a bleaching agent and an amide-substituted bleachactivator, wherein said bleach activator is present as a divalent metalsalt, a trivalent Al salt, a mixed metal salt whereby at least one ofthe salts is a divalent metal salt or trivalent Al salt, or mixturesthereof.
 2. A nonaqueous detergent composition according to claim 1wherein said divalent salt is selected from Ca and/or Mg.
 3. Anonaqueous detergent composition according to claim 1 wherein said mixedmetal salt comprises a monovalent metal.
 4. A nonaqueous detergentcomposition according to claim 1 wherein said amide substituted bleachactivator is selected from the group consisting of amide-substitutedbleach activators having the following formula: ##STR6## and mixturesthereof; wherein R¹ is an alkyl, aryl or alkaryl group containing fromabout 1 to about 14 carbon atoms, R² is an alkylene, arylene oralkarylene group containing from about 1 to 14 carbon atoms, R⁵ is H oran alkyl, aryl or alkaryl group containing from about 1 to about 10carbon atoms, and L is any suitable leaving group which is capable ofbeing displaced from said bleach activator as a consequence of anucleophilic attack on said bleach activator by a perhydroxide anion. 5.A nonaqueous detergent composition according to claim 1 wherein saidamide-substituted bleach activator is selected from the group consistingof: 4- N-octanoyl-6-aminohexanoyloxy!benzene sulfonate, 4-N-nonanoyl-6-aminohexanoyloxy!benzene sulfonate, 4-N-decanoyl-6-aminohexanoyloxy!benzene sulfonate and mixtures thereof. 6.A nonaqueous detergent composition according to claim 1 wherein saidbleaching agent is percarbonate.
 7. A nonaqueous detergent compositionwhich is in the form of a liquid, paste or gel, said nonaqueousdetergent composition comprising a bleaching agent and a bleachactivator, wherein said bleach activator is present as a trivalent Alsalt, a mixed metal salt whereby at least one of the salts is atrivalent Al salt, or mixtures thereof.
 8. A nonaqueous detergentcomposition according to claim 7 wherein said mixed metal salt comprisesa monovalent salt.
 9. A nonaqueous detergent composition according toclaim 7 wherein said mixed metal salt comprises a divalent salt.
 10. Anonaqueous detergent composition according to claim 7 wherein saidbleaching agent is percarbonate.